Anthracene dye and process of making same.



No. 753,657. Patented March 1, 1904.

UNITED STATES, PATENT OFFICE.

OSCAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOR TO THE BADISOHE ANILIN &SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE, GER- MANY, A CORPORATIONOFBADEN.

ANTHRACENE DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 753,657, dated March 1,1904.

Application filed December 19, 1900. Serial No. 40,446; (Specimens) Towhom it y con/087%" anthraquinone substance, and the halogen- 25 Be itknown that I, OSCAR BALLY, doctor of containing derivatives of which Idesire to philosophy and chemist, a citizen of the Swiss have understoodas being included in the Republic, residing at Mannheim, in the Grandgeneric term halogenated amido-anthra'qui- 5 Duchy of Baden, Germany,have invented none substance. For the broad purpose of new and usefulImprovements in Anthraoene my invention I may take a hereinbefore-de- 3Dyes and Processes of Making the Same, of fined amido-anthraquinonesubstance, subject which the following is a specification. the same to asuitable halogenation operation,

It is known that the amido derivatives of and may then subject theresulting haloge- IO anthraquinone and derivatives thereof, as alsonated amido-anthraquinone substance to the their substituted amidoderivatives and the action of ammonia or of agents which pro- 35sulfo-acids of these bodies, can be converted duce ammonia during thecourse of the reacinto halogen derivatives by treatment with tion. Inthis way coloring-matters are obhalogen or halogenizing agents. It isfurtained which can either be used at once in 5 ther known that thesehalogen derivatives redyeing or after previous sulfonation, and the actwith aromatic amins, giving new coloringdyed goods possess a high degreeof fastnes's. 4 matters. Various products are obtained, according to Inthis my inventionI make use of halogenthe quantity of halogen employedin the halocontaining products, such as can be obtained genizingprocess, as also to the conditions ob 20 by suitable halogenation ofeither monoor served during this operation. As instances di-amidoormonoor di-alphyl-amido-anthraof these variations I give the propertiesof 45 quinone or sulfo-acids of the same, which subsome of the saidhalogen'derivatives that can stances I desire hereinafter to beunderstood be obtained according to this invention in the as beingincluded in the generic term amidofollowing table:

In sulfuric acid and bortzeic acid t: a m era- Halogen derlvatlveobtained Solution in alcoa In moderately- I Solution m water. hoL Insulfunc acid. gar: 32311612 1:11; warm anflm grees centigrade.

Ten (10) parts alpha-anilido- Red-orange. Orange. Brown. Brown. Brownishorange. anthraquinone monosulfo acid and sixteen (16) parts bromin inconcentrated aqueous suspension.

Ten (10) parts beta-anilido-an- Cherry-red. Brown-red. Brown.Red-violet. Brownish cherry thraquinone monosulfo-acid and red. sixteen(16) parts bromin in concentrated aqueous suspension.

Ten (10) parts beta-aniIido-an- Red-orange. Orange-yellow. Red-brown.Fuchsin-red. Brown. thraquinone monosulfo-aeid and sixteen (16) parts ofbromin in dilute aqueous solution.

Ten (10) parts crude (alphaand Violet-red. Brown-red. Olive. Red-violet.Cherry-red. beta mixed) anilido-anthraquinone monosulfo-acid and eight(8) parts of bromin.

The same with twelve (12) parts Violet-red. Brown-red. Brown.Red-violet. Cherry-red. of bromin.

In sulfuric acid aFd boracic acid z I tempera- Halogen derivativeobtained Solut1on 1n alco- In moderatelyfro Solution 1n water. hoL Insulfuric acld. e1ot1%% )111(11% warm 2mm.

grees centigrade.

The same with sixteen (16) Cherry-red. Brown-red. Yellow-brown.Fuchsin-red. Brownish cherryparts of bromin. d.

The same with thirty two (32) Yellow-red. Recidish yellow. Reddishbrown. Carmine-red. Yellow-brown. parts of bromin.

Ten (10) parts paratoluidin- Cherry-red. Yellow-red. Green-olive.Red-violet. Red-brown. anthra uinone sulfo-acitLtwo (2) parts 0potassium chlorate, and fifteen (15) parts of fuming hydrochloric acid.

The following examples will serve to illustrate the manner in which myinvention may be carried into practical eflect; but the invention is notconfined to the instances exemplified nor to the conditions given in theexamples. The parts are by weight.

Example 1: Suspend ten (10) parts of crude anilido-anthraquinonemonosulfoacid (alpha and beta mixed) in about two hundred (200) parts ofwater. Treat the mixture at ordinary temperature with twelve (12) partsof bromin and stir well for about twelve (12) hours. Add commonsalt orpotassium chlorid and filter off the bromid formed. Collect and dry inthe usual way. Next mix in an autoclave ten (10) parts of thebrom-anilidoanthraquinone monosulfo acid so obtained with fifty parts ofaqueous ammonia, (containing about twenty (20) per cent. NH3.) Heat thismixture in the autoclave for about six (6)hours at a temperature ofabout two hundred (200)degrees centigrade. Allow it to cool andprecipitate the reaction product by means of common salt. Collect thecoloring-matter by filtration, press and dry, or preserve for use in theform of paste. The coloring-matter dyes chrome mordanted wool gray-blueto blue-black shades. The coloring-matter is easily soluble in water,giving a brownishviolet solution, which is not changed in color bycaustic soda or by sodium carbonate. With concentrated sulfuric acid itgives a brown color.

The product obtained when using the isolated alpha or beta compoundsinstead of the mixture as prescribed above possesses similar properties.1

Example 2: Prepare the brom-anilido-anthraquinone monosulfo-acid asdescribed in the foregoing Example 1, but using sixteen (16) parts ofbromin instead of twelve (12) parts. Mix ten (10) parts of thebromination product so obtained with about seventy (7 0) parts ofaqueous ammonia (containing about twenty (20) per cent. NH3) and heatthe mixture in an autoclave for about nine (9) hours at a temperature ofabout one hundred and sixty (160) degrees centigrade. Precipitate thecoloring-matter by means of common salt and collect in the usual way.The coloring-matter 5 0 so obtained dyes chrome mordanted woolgray-violet to violet-black shades. In a similar manner coloring-matterscan be obtained from other brominated or chlorinated derivatives ofanilido-anthraquinone sulfo-acid and of the otheralphylido-anthraquinone sulfoacids. In quite an analogous mannercoloring-matters can be obtained from halogen derivatives ofdialphyl-diamido-anthraquinone sulfo-acid. The said halogen derivativesare new and can be obtained by moderate treatment of the said sulfo-acidwith halogen. The production of the coloring-matters from halogenderivatives can be effected according to the data of the foregoingexamples. Similarly coloring-matters are obtained from halogensubstituted amidoor diamido-anthraquinone sulfo-acids ortheircorresponding unsulfonated compounds. Such products do not possess thedesired solubility in water, but 7 are more soluble on sulfonation.

Now what I claim is-- 1. The process of making anthracene dye whichconsists in acting upon ahereinbeforedefined amido-anthraquinonesubstance with halogen and then with ammonia.

2. The process of making anthracene dye which consists in acting upon ahereinbeforedefined amido-anthraquinone substance with bromin and thenwith ammonia.

3. The process 01": making anthracene dye which consists in acting uponone part of a hereinbefore defined amido anthraquinone substance withtwelve (12) parts of bromin and then with ammonia.

4:. The process of making anthracene dye which consists in acting upon amixture of crude alphaand beta-anilido-anthraquinone monosulfo-acid withhalogen and then with ammonia.

5. The process of making anthracene dye which consists in acting upon amixture of' crude alphaand beta-anilido-anthraquinone monosulfo-acidwith bromin and then with ammonia.

6. The process of making anthracene dye which consists in acting uponone part of a mixture of crude alphaand beta-anilido-anthraquinonemonosulfo-acid with twelve (12) parts of bromin and then with ammonia.

7. The process of makinganthracene dye which consists in acting upon amixture of halogenated alphaand beta-anilido-anthraquinonemonosulfo-acid with ammonia.

8. The process of making anthracene dye which consists in acting upon amixture of brominated alphaand beta-anilid o-anthraquinonemonosulfo-acid with ammonia.

9. As a new article of manufacture the col- Min -matter which can bemade from halo genated crude alphaand beta-anilido-anthraquinonemonosulfo-acid and ammonia which is soluble in water and which dyeschrome mordanted wool in shades which are within the range of gray-blueto blue-black.

10. As a new article of manufacture the coloring-matter which can bemade from brominated crude alphaand betaanilidoanthraquinonemonosulfo-acid and ammonia which ter giving a solution of brown-violetcolor,,

which is not affected in color by caustic soda or by carbonate of soda,and which gives a brown color with concentrated sulfuric acid.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses. OSCAR BALLY.

Viitnesses: 7

ERNEST F. EHRHARDT, MAX H. EsLEo.

